CN1739214A - Electrolyte for use in phosphate based lithium ion/polymer cells - Google Patents

Electrolyte for use in phosphate based lithium ion/polymer cells Download PDF

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CN1739214A
CN1739214A CNA2004800024316A CN200480002431A CN1739214A CN 1739214 A CN1739214 A CN 1739214A CN A2004800024316 A CNA2004800024316 A CN A2004800024316A CN 200480002431 A CN200480002431 A CN 200480002431A CN 1739214 A CN1739214 A CN 1739214A
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carbonic acid
battery pack
ester
electrolyte
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CN100372162C (en
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艾琳·赛德埃
乔恩·帕克
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WILLENS TECHNOLOGIES Inc
Valence Technology Inc
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

This invention relates to electrolytes containing ethyl methyl carbonate as a solvent for use in lithium cells or batteries containing metal phosphate cathodes. The invention further relates to electrolytes comprising ethyl methyl carbonate, ethylene carbonate, diethyl carbonate and propylene carbonate for use in lithium cells or batteries with metal phosphate cathodes, and to batteries employing such electrolytes. The electrolytes of the present invention are an improvement over other electrolytes used in lithium cells or batteries with metal phosphate cathodes in that the electrolytes are less prone to gassing and therefore have better shelf stability.

Description

A kind of being used in based on the electrolyte in the phosphatic lithium ion/polymer cells
Technical field
The present invention relates to a kind of being used on the lithium battery group, contain the electrolyte of carbonic acid ethyl-methyl ester solvent, this lithium battery group comprises lithium metal, lithium ion and the lithium ion polymer battery pack with metal phosphate negative electrode.The invention further relates to a kind of being used on the lithium battery group, the electrolyte that comprises ethylmethyl carbonate, carbonic acid ethylidene ester, carbonic acid diethyl ester and propylene carbonate, this lithium battery group comprises lithium metal, lithium ion and the lithium ion polymer battery pack with metal phosphate negative electrode, also relates to using these electrolytical battery pack.Electrolyte of the present invention is better than other used electrolyte of lithium battery group with metal phosphate negative electrode, and this is because electrolyte of the present invention is difficult for bubbling thereby has better storage stability.
Background technology
Being extensive use of of portable electric appts such as mobile phone and portable computer produced the very big demand to high power capacity, long-life lightweight battery pack thereupon.Thereby alkali metal batteries, especially lithium ion battery are formed for a kind of useful suitable energy.Lithium metal, sodium metal and magnesium metal battery group also are the known suitable energy.
In general, the lithium battery group is to be prepared by one or more lithium electrochemical cells that contain electro-chemical activity (electroactive) material.These batteries comprise negative electrode, positive electrode and the electrolyte between positive and negative electrode usually at least.
The lithium ion battery group is known in the field.The lithium ion battery group has the insertion anode, for example lithium metal chalcogenide, lithium metal oxide, coke and graphite.The electrode of these types uses with the insertion negative electrode that contains lithium usually, forms electroactive right in the battery.Resulting battery is uncharged in initial condition.Before these batteries are used to supply electrochemical energy, then must charge.In charging process, lithium migrates to negative electrode from the electrode cathode that contains lithium.In discharge process, lithium then is back to positive electrode from the negative electrode migration.In the charging process once more afterwards, lithium migrates to the negative pole place that it inserts once more again.Therefore, in each charge/discharge cycle, lithium ion (Li+) moves between electrode.This rechargeable battery pack is called as chargeable lithium ion battery group or rocking chair battery pack.
Successful lithium ion battery group need adopt the electrolyte of high ion-conductivity, so that keep superperformance reasonably discharging and recharging under the speed.Electrolyte must be an electrochemical stability, has acceptable cycle life simultaneously, has storage stability, and saves cost.The performance of lithium ion battery group is subjected to the influence of electrolyte quality very big.Therefore, battery industry is making great efforts to improve electrolytical quality and characteristic always.
In traditional lithium ion battery group, the carbonic ester that has adopted various linearities and annular is as electrolyte solvent.When forming electrolyte with suitable solute, these electrolyte generally all have ionic conductivity relatively preferably.Usually, these electrolyte are made up of the slaine that is dispersed in nonaqueous solvents or the polymer.For example, in the electrolyte of dimethyl carbonate through being commonly used in the lithium ion battery group.It has quite low viscosity, can be used as viscosity reducers thereby conductibility improving agent just.But dimethyl carbonate can be reacted on the carbon anode of lithiumation, forms the accessory substance of gaseous state.This especially has in the battery of flexible package at battery be a problem.Usually claim that this problem is the bubbling phenomenon.
Probe into the unfavorable side reaction that takes place between this class and the battery component and the research of reaction mechanism is all carrying out always.The researcher also in that selection is low with the battery component reactivity as possible, can keep the solvent and the salt of battery performance simultaneously again.Determine to prevent the method for unfavorable side reaction, prevent that especially the method for formation gas in containing the battery of lithium metal phosphate cathodes from being very challenging.
Thereby the researcher is seeking other high conductance electrolyte that can be used in the current battery group always.Electrolytical advantage of the present invention is that it can avoid the bubbling phenomenon in containing the battery of lithium metal phosphate cathodes, keeps high conductance and good chemistry and thermal stability simultaneously.
Summary of the invention
The present invention relates to a kind of being used on the lithium battery group, contain the electrolyte of carbonic acid ethyl-methyl ester solvent, this lithium battery group comprises lithium metal, lithium ion and the lithium ion polymer battery pack with metal phosphate negative electrode.The invention further relates to a kind of being used on the lithium battery group, the electrolyte that comprises the four component solvent systems that form by ethylmethyl carbonate (EMC), carbonic acid ethylidene ester (EC), carbonic acid diethyl ester (DEC) and propylene carbonate (PC), this lithium battery group comprises lithium metal battery group, lithium ion battery group and the lithium ion polymer battery pack with metal phosphate negative electrode, also relates to using these electrolytical battery pack.Electrolyte of the present invention is better than having other used in the lithium battery group of metal phosphate negative electrode electrolyte, because electrolyte of the present invention is difficult for bubbling thereby has better storage stability.
The preferred embodiment of the present invention relates to a kind of electrolyte that comprises slaine and four solvent systems, and wherein four solvent systems are made up of carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate.The amount of carbonic acid ethylidene ester is preferably about 20-80wt%.Propylene carbonate is preferably measured and is about 0-20wt%.The amount of ethylmethyl carbonate is preferably about 10-80wt%, and the amount of carbonic acid diethyl ester is preferably about 0-30wt%.(these four kinds of percentages of ingredients are to represent with the percentage by weight of four kinds of component solvent.These four kinds of components % as used herein are four kinds of percentage by weights that component solvent is in use adopted.) this electrolyte has high conductance, and can reduce the formed gaseous by-product of unfavorable side reaction between electrolyte and other composition of battery pack.
The invention still further relates to and contain electrolytical battery pack of the present invention or battery.Negative electrode in these battery pack and the battery comprises metal phosphate, is more preferably lithium metal phosphates.The preferred implementation of the negative electrode that the present invention is used is that the active material of negative electrode is LiMg xFe 1-xPO 4Or lithium vanadium phosphate active material, wherein x is greater than about 0.01 and less than about 0.15.
Brief Description Of Drawings
Fig. 1 represents the cycle performance of electrolyte solution of the present invention.
Fig. 2 represents to use electrolysis mass-energy of the present invention to reach acceptable cycle life.
Detailed Description Of The Invention
As mentioned above, the present invention relates to a kind of being used on the lithium battery group, contain the electrolyte of carbonic acid ethyl-methyl ester solvent, this lithium battery group comprises lithium metal, lithium ion and the lithium ion polymer battery group with metal phosphate negative electrode. The invention further relates to a kind of being used on the lithium battery group with metal phosphate negative electrode, the electrolyte that comprises the four component solvent systems that are comprised of ethylmethyl carbonate (EMC), carbonic acid ethylidene ester (EC), carbonic acid diethyl ester (DEC) and carbonic acid propylidene ester (PC) also relates to and uses these electrolytical battery pack. Electrolyte of the present invention is better than having other used in the lithium battery group of metal phosphate negative electrode electrolyte, because electrolyte of the present invention is difficult for bubbling thereby has better storage stability.
The preferred embodiment of the present invention relates to a kind of electrolyte that comprises slaine and four solvent systems, and wherein four solvent systems are comprised of carbonic acid ethylidene ester, carbonic acid propylidene ester, carbonic acid diethyl ester and ethylmethyl carbonate. The amount of carbonic acid ethylidene ester is preferably about 20-80 (wt) %. Carbonic acid propylidene ester is preferably measured and is about 0-20wt%. The amount of ethylmethyl carbonate is preferably about 10-80wt%, and the amount of carbonic acid diethyl ester is preferably about 0-30wt%. This electrolyte has high conductance, and can reduce the formed gaseous by-product of unfavorable side reaction between electrolyte and other composition of battery pack.
The invention still further relates to and contain the electrolytical battery pack of the present invention or battery. Negative electrode in these battery pack and the battery comprises metal phosphate, is more preferably the lithium metal phosphate. The preferred embodiment of the negative electrode that the present invention is used is that the cathode activity material is LiMgxFe 1-xPO 4Or lithium vanadium phosphate active material, wherein 0.01≤x≤0.15.
Dimethyl carbonate is everlasting and is used as viscosity reducers in the electrolyte of lithium battery group and improves conductibility.But the boiling point of dimethyl carbonate is low, and can react on the carbon anode of lithiumation, forms gas CH 4And C 2H 6This can bring problem in the battery of flexible package, because gas content will is in flexible package, a large amount of emitting steeped oneself-meeting and caused packing distortion or explosion.
Ethylmethyl carbonate (EMC) is also referred to as carbonic acid Methylethyl ester (MEC), and its volatility is less than dimethyl carbonate.EMC is difficult for cracking thereby is difficult for producing bubble.But the researcher finds that in all batteries directly replacing dimethyl carbonate with the carbonic ester of long-chain more all fails, and this is because of causing negative effect to the periodic duty performance when this replacement of use.For example, the problem with carbonic acid diethyl ester replacement dimethyl carbonate is in lithium ion battery: show unacceptable battery capacity and descend during cycle life.
The lithium ion battery group is because high electrochemical potential and high performance nature that it had, thereby represented a development branch in the battery industry.Some lithium ion and lithium ion polymer battery pack also show high-energy-density, high voltage and good pulse performance.
The example of a specific lithium ion battery group is the lithium ion polymer battery pack of a kind of use based on phosphatic cathode material.This battery pack shows that high-energy-density, high efficiency, cost are low, safety and the feature of environmental protection.Developed this phosphate at present, it is compared existing battery material and has lot of advantages.
Develop this based on phosphatic cathode material before, the battery chemistries of lithium ion battery group is subject to selects suitable lithium to discharge cathode material, that is, three kinds of oxide electroactive materials, LiMn 2O 4, LiCoO 2And LiNiO 2Although the manufacturing cost of these materials is very high, find that usually they have very high chemical property.
Used phosphate material can divide for by one or more phosphate groups (PO in the battery pack of the present invention 4) material that makes of tetrahedron, or by several PO 4Group is shared one, two or three oxygen and material that condensation makes.When adopting for example F, Cl, S and H atom to replace one or more oxygen atom in the phosphate, obtained the phosphate that replaces.
The phosphate of common form, monophosphate is from orthophosphoric acid H 3PO 4The salt of deriving.The feature of these salt is to have independently PO 4 3-Group, this group comprise four oxygen atoms that are positioned at each place, angle of tetrahedron of primitive rule around the phosphorus atoms that is positioned at the center and the phosphorus atoms.The physics of monophosphate and chemical property are open by document, and think that this class material has chemistry and calorifics stability.
Another kind of monophosphate is a transition metal phosphate.At present, begun these transition metal phosphates, especially the lithiumation metal phosphate is used as the active material of cathode of lithium ion battery group.The oxide of these transition metal phosphates and their correspondences is the same to be the compound of insert type.
Transition metal phosphate can make the design of lithium ion battery group have very big flexibility.Only just can adjust the voltage and the specific capacity of active material by changing transition metal itself.These active materials are USSN 09/484799 (on January 18th, 2000 submitted), USSN09/484919 (on January 18th, 2000 submitted), USSN 10/116276 (on April 3rd, 2002 submitted), on the books among USSN 10/116450 (on April 3rd, 2002 submitted) and the USSN 10/115802 (on April 3rd, 2002 submitted).The used elements doped lithium metal phosphate of the present invention includes but not limited to the U.S.6 that authorized on May 14th, 2002,387,568 and the USSN 10/014822 that submits October 26 calendar year 2001 in disclosed lithium metal phosphates.The transition metal phosphate of a kind of particular type that the present invention is used, promptly the lithium vanadium phosphate includes but not limited to disclosed lithium vanadium phosphate in the following document: the U.S.5 that on February 16th, 1999 authorized, 871,866, the U.S.5 that on June 1st, 1999 authorized, 908,716, the U.S.6 that on October 24th, 2000 authorized, the U.S.6 that on October 28th, 136,472,2000 authorized, 153, the U.S.6 that on May 14th, 333,2002 authorized, 387,568, the U.S.6 that on September 10th, 2002 authorized, 447,951, July 26 calendar year 2001, the disclosed WO01/54212 and the USSN that submits 10/014822 in October 26 calendar year 2001 were incorporated herein by reference these documents.Also can use the physical mixture of all above-mentioned active cathode materials of enumerating.Most preferred active material of cathode is to have general formula LiFe 1-xMgXPO 4Material, wherein for about 0.01-0.15.Other preferred active material of cathode is lithium vanadium phosphate material such as Li 3V 2(PO 4) 3, or general formula is LiM xFe 1-xPO 4Material, wherein M selects Zr, Ti, Nb, Mg, Zn and Ca.
Can eliminate in the battery cell free liquid, the battery pack that adopts transition metal phosphate and thermoplastic polymer electrolyte to make is referred to herein as lithium ion polymer battery pack.This battery pack is not owing to contain liquid electrolyte, thereby can be with packaged in foil.This package design be owing to can significantly reduce battery weight and increase design flexibility, thereby has significant advantage.
Recently, the battery pack that adopts lithium transition metal phosphates and electrolyte to make is easy to bubbling in flexible package, and wherein electrolyte is by carbonic acid ethylidene ester and the dimethyl carbonate and the 1MLiPF of 2: 1 weight ratios 6Salt is formed.The researcher has found the whole bag of tricks to correct this problem.A kind of method is to use ethylmethyl carbonate and eliminates the use of dimethyl carbonate.The volatility of ethylmethyl carbonate is lower than dimethyl carbonate, and is difficult for cracking and produces bubble.
Other experiment has caused the electrolytical discovery of the present invention's four solvent systems, and it can be used as electrolyte in this metalloid phosphate battery pack.With the carbonic ester of long-chain more for example ethylmethyl carbonate to replace dimethyl carbonate often unsuccessful, reason is to cause cycle performance to descend.But, find that now ethylmethyl carbonate can successfully replace dimethyl carbonate in metal phosphate battery, and cycle performance is descended.Ethylmethyl carbonate now successfully is used for the lithium metal phosphate battery, and keeps conductive performance and battery performance.
Following term and abbreviation have following definition and implication:
DEC: carbonic acid diethyl ester
DMC: dimethyl carbonate
EC: carbonic acid ethylidene ester
EMC: ethylmethyl carbonate (=MEC)
MEC: carbonic acid Methylethyl ester (=EMC)
PC: propylene carbonate
μ m: micron
Wt: weight
" battery pack " as herein described is meant a kind of one or more electrochemical cells that comprise, and is used to produce the device of electric current.Each electrochemical cell comprises anode, negative electrode and electrolyte.
Term of the present invention " anode " and " negative electrode " are meant the electrode that oxidation and reduction reaction can take place respectively in the battery power discharge process.In the batteries charging process, the position of oxidation and reduction reaction is reversed.
Term " preferably " is meant the embodiment of the present invention that has certain benefits under given conditions.But other execution mode also can be preferred under identical or other condition.In addition, for the enumerating and do not mean that other execution mode is unhelpful of one or more preferred implementations, other execution mode is not got rid of from scope of the present invention.
Electrolyte
Electrolyte of the present invention adopts conventional method to make by those of ordinary skill in the art.In general, the present invention relates to a kind of electrolyte that comprises ethylmethyl carbonate, this electrolysis mass-energy is used in the battery pack of containing metal phosphate negative electrode.The invention further relates to a kind of battery pack of using this electrolytical containing metal phosphate negative electrode.Especially, electrolyte of the present invention comprises ethylmethyl carbonate, carbonic acid ethylidene ester, carbonic acid diethyl ester and propylene carbonate.
The amount of carbonic acid ethylidene ester is preferably about 20-80wt%.Propylene carbonate is preferably measured and is about 0-20wt%.The amount of ethylmethyl carbonate is preferably about 10-80wt%, and the amount of carbonic acid diethyl ester is preferably about 0-30wt%.More preferably, the amount of ethylmethyl carbonate is about 10-40wt%; The amount of carbonic acid ethylidene ester is about 30-70wt%; Propylene carbonate is preferably measured and is about 2-20wt%; The amount of carbonic acid diethyl ester is about 2-30wt%.In another preferred embodiment, the amount of ethylmethyl carbonate is about 10-30wt%; The amount of carbonic acid ethylidene ester is about 50-70wt%; Propylene carbonate is preferably measured and is about 2-10wt%; The amount of carbonic acid diethyl ester is about 5-30wt%.
In another preferred embodiment, the amount of ethylmethyl carbonate is about 25wt%; The amount of carbonic acid ethylidene ester is about 60wt%; Propylene carbonate is preferably measured and is about 5wt%; The amount of carbonic acid diethyl ester is about 10wt%.In another preferred embodiment, the amount of ethylmethyl carbonate is about 10wt%; The amount of carbonic acid ethylidene ester is about 60wt%; Propylene carbonate is preferably measured and is about 5wt%; The amount of carbonic acid diethyl ester is about 25wt%.In another preferred embodiment, the amount of ethylmethyl carbonate is about 30wt%; The amount of carbonic acid ethylidene ester is about 60wt%; Propylene carbonate is preferably measured and is about 5wt%; The amount of carbonic acid diethyl ester is about 5wt%.
In general, the electrolytic cell of polymerization comprises polymeric film composition electrodes and barrier film.Especially, the rechargeable lithium battary Battery pack comprises a kind of separator through the electrolyte plasticizing.In the charge and discharge cycles of battery, lithium ion can pass these polymer dielectrics and move between electrode.In these batteries, ionogenic electrode is that lithium compound or other can insert the material of lithium ion.Electrolysis mass-energy of the present invention is used as active material in containing the battery of transition metal, more preferably be used as active material in the phosphatic battery of lithium-containing transition metal.Active material is preferably lithium vanadium phosphate and LiMg xFe 1-xPO 4, wherein x is about 0.01-0.15.
The electrode isolation film comprises polymer substrate, and this matrix provides the organic solution of the separable lithium salts (solute) of ion transport to obtain ionic conductibility by adding.Keep the electrolyte lithium salt solution in the separator material of high-intensity pliability polymerization electrolytic cell, and in very wide temperature range, had function.These electrolytic films can adopt conventional mode as the separator in the battery cell parts of machinery assembling, perhaps are used in the continuous coated composite battery Battery pack that constitutes by electrode and electrolyte composition.
Electrolyte meter of the present invention reveals high conductance, good chemical stability, favorable mechanical characteristic, good thermal stability and hypotoxicity.Loop test has shown that electrolysis mass-energy of the present invention is used for having the lithium battery group of the negative electrode that is made of electroactive metal phosphate.
Disclosed battery pack in the patent that can use the lamellar battery pack of this electrolytical typical case to comprise but be not limited to above enumerate.For example, typical double cell comprises negative electrode, positive electrode and another negative electrode, and wherein electrolyte/separator places between each counterelectrode.Negative electrode and positive electrode all contain current-collector.Negative electrode comprises the insertion material that is dispersed in the polymeric binder matrix, as carbon or graphite or low voltage lithium insertion compound, also comprises current-collector, preferably copper collector foil, the preferred unlimited net grid form that is inserted into or places negative electrode one side that adopts.Separator is placed on the negative electrode opposite side with the current-collector position opposite.The positive electrode of containing metal phosphate active material is placed on the separator opposite side with the negative electrode position opposite.With current-collector, preferred aluminium foil or aluminium net grid, be placed on positive electrode on the opposite side of separator position opposite.Another separator is placed on a side with second current-collector position opposite, then another negative electrode is placed on this separator.Employing well known to a person skilled in the art that conventional method is distributed to electrolyte in the battery.With cell sealing, prevent the infiltration of air and moisture with the packaging material of protectiveness.In other execution mode, two positive electrodes can be used to replace two negative electrodes, and like this, negative electrode is just replaced by positive electrode.
The lithium salts that disperses in electrolyte (solute) is including but not limited to LiBF 4, LiBF 6, LiAsF 6, LiPF 6, LiClO 4, LiB (C 6H 5) 4, LiAlCl 4, LiB r, LiB (C 6H 5) 4, LiAlCl 4, LiCF 3SO 3, LiN (CF 3SO 2) 2, LiC (CF 3SO 2) 3, LiN (SO 2C 2F 5) 2, Li[B (O 4C 2)] 2And composition thereof.Typical alkali metal salt used in this invention is including but not limited to having formula M +X -Salt, wherein be M +Li for example +, Na +, K +And the alkali metal cation of combination; Be X -Be anion, Cl for example -, Br -, I -, ClO 4-, BF 4-, PF 6-, AsF 6-, SbF 6-, CH 3CO 2-, CF 3SO 3-, N (CF 3SO2) 2-, N (CF 3SO2) 2-, C (CF 3SO2) 2-And combination.Lithium salts is preferably LiBF 4Or LiPF 6
The used anode material of battery pack of the present invention is including but not limited to lithium, carbon, graphite, CMS graphite (Shanghai Shanshan Technology), coke, meso carbon, tungsten oxide, titanate, metal oxide (especially transition metal oxide), metal phosphate (especially transition metal phosphate), sulfate, silicate, vanadate, metal chalcogenide and lithium alloy, the alloy of lithium and aluminium, mercury, manganese, iron and zinc for example, and their physics and chemical mixture.Preferred anode material is CMS graphite or carbon, for example coke or graphite, especially MCMB: mesophase-carbon micro-beads (Osaka Gas Company, Limited, Japan) and MCF: based on the carbon fiber of mesophase pitch (Petoca Corporation Limited, Japan).But the compatible electroactive anode material of any and disclosed electrolyte all can adopt.
The active cathode material that can be used on the battery pack of the present invention comprises transition metal phosphate, more preferably lithium transition metal phosphates.Preferred cathode material is a transition metal phosphate, include but not limited to disclosed transition metal phosphate in the following document: 2000 1 about USSN that submitted in 18th 09/484799,2000 1 about USSN09/484919 that submitted in 18th, the USSN10/116276 that on April 3rd, 2002 submitted, the USSN 10/115802 that the USSN 10/116450 that on April 3rd, 2002 submitted and on April 3rd, 2002 submit.Other preferred cathode material is the lithium vanadium phosphate, includes but not limited to the disclosed lithium vanadium phosphate of following document: the U.S.5 that on February 16th, 1999 authorized, 871,866, the U.S.5 that on June 1st, 1999 authorized, 908,716, the U.S.6 that on October 24th, 2000 authorized, the U.S.6 that on October 28th, 136,472,2000 authorized, 153, the U.S.6 that on May 14th, 333,2002 authorized, 387,568, the U.S.6 that on September 10th, 2002 authorized, 447,951, July 26 calendar year 2001 disclosed WO01/54212, the USSN that submits 10/014822 in October 26 calendar year 2001.The physical mixture of all above-mentioned active cathode materials of enumerating all can use.Most preferred active material of cathode is to have general formula LiFe 1-xMg xPO 4Material, wherein x is between about 0.01 to 0.15.Other preferred active material of cathode is a lithium vanadium phosphate material, or general formula is LiMFePO 4Material, wherein M is selected from Zr, Ti, Nb, Mg and Ca.
The material that the conductive filler that adopts in the battery pack of the present invention is included, can be particle, conductivity ceramics, conductive fiber, conducting polymer (for example having two key conjugate networks) of for example carbon black, graphite, nickel powder, metallic particles, washing etc. as polypyrrole and polyacetylene.Preferred conductive filler is a carbon black.
Current-collector is that battery art is known, and any current-collector that can be used on the battery pack can both be used for preparing battery pack of the present invention and battery.
Embodiment
Carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate all are commercially available solvents.EC, PC, DEC and EMC mix with following weight ratio, thereby obtain as electrolytical solvent.Adopt lithium hexafluoro phosphate as electrolytical solute, gained concentration is 1M.
Weight % (1M LiPF 6)
EC PC DEC EMC
60 5 10 25
60 5 5 30
60 5 25 10
60 0 0 33
60 0 20 20
60 0 10 30
60 0 30 10
Then, prepare film-type polymerization cell group according to following method.An independent standard cathode mould is online to aluminium, be coated with then and be covered with adhesion promoter.Similarly, an independent standard anode mould to copper mesh, is coated with then and is covered with adhesion promoter.The each several part of these assemblies makes electrode through punching press (punch out).Press separating film layer between two anode electrodes and a cathode electrode, form the assembly that anode/separator/cathode/separator/anode links to each other, this assembly is called as double cell.In addition, can prepare double cell with two negative electrodes and an anode.
A complete battery also can comprise one or more double cells that are welded together in parallel.
Battery is removed drying then.Add electrolyte of the present invention then, added electrolytical amount can make it be aggregated thing to absorb fully, thereby does not have residual electrolyte in battery.Then with packaging material with cell sealing.
At constant current is that 2.6A and termination are charged and the voltage of discharge is respectively under the situation of 3.65V and 2.5V, and the charge and discharge cycles of electric charge repeats 600 times.
Fig. 1 adopts above-mentioned electrolyte to carry out the result of loop test.Fig. 1 shows that the cycle life of battery is subjected to negative effect when directly replacing DMC with DEC, because the capacity that battery keeps after 100 circulations greatly reduces.As can be seen from Figure 1, replace the impact effect of DMC littler, have acceptable performance in some cases with EMC.
Fig. 2 shows, uses the preferred electrolyte formula of the present invention, also can reach acceptable cycle life even removed DMC from solvent mixture.
To those of ordinary skills obviously as can be known various modifications, replacement and change all within the scope of the invention and invention flesh and blood.Record of the present invention is exemplary only the time, thereby the various changes that do not break away from essence of the present invention all fall in the scope of the invention.

Claims (61)

1. one kind is used in lithium battery with lithium metal phosphate cathodes or the electrolyte in the battery pack, and wherein, this electrolyte comprises slaine and ethylmethyl carbonate, propylene carbonate, carbonic acid diethyl ester and carbonic acid ethylidene ester.
2. electrolyte according to claim 1, wherein, the amount of this ethylmethyl carbonate is about 10 to about 80wt%.
3. electrolyte according to claim 2, wherein, the amount of this carbonic acid ethylidene ester is about 20 to about 80wt%.
4. electrolyte according to claim 3, wherein, the amount of this propylene carbonate is about 0 to about 20wt%.
5. electrolyte according to claim 4, wherein, the amount of this carbonic acid diethyl ester is about 0 to about 30wt%.
6. electrolyte according to claim 1, wherein, the amount of this ethylmethyl carbonate is about 10 to about 40wt%.
7. electrolyte according to claim 6, wherein, the amount of this carbonic acid ethylidene ester is about 30 to about 70wt%.
8. electrolyte according to claim 6, wherein, the amount of this carbonic acid ethylidene ester is about 50 to about 70wt%.
9. electrolyte according to claim 7, wherein, the amount of this propylene carbonate is about 2 to about 10wt%.
10. electrolyte according to claim 9, wherein, the amount of this propylene carbonate is about 5wt%.
11. electrolyte according to claim 9, wherein, the amount of this carbonic acid diethyl ester is about 5 to about 30wt%.
12. electrolyte according to claim 1, wherein, the amount of this carbonic acid ethylidene ester is about 60wt%, and the amount of this propylene carbonate is about 5wt%, and the amount of this carbonic acid diethyl ester is about 10wt%, and the amount of this ethylmethyl carbonate is about 25wt%.
13. electrolyte according to claim 1, wherein, the amount of this carbonic acid ethylidene ester is about 60wt%, and the amount of this propylene carbonate is about 5wt%, and the amount of this carbonic acid diethyl ester is about 25wt%, and the amount of this ethylmethyl carbonate is about 10wt%.
14. electrolyte according to claim 1, wherein, the amount of this carbonic acid ethylidene ester is about 60wt%, and the amount of this propylene carbonate is about 5wt%, and the amount of this carbonic acid diethyl ester is about 5wt%, and the amount of this ethylmethyl carbonate is about 30wt%.
15. lithium battery or battery pack, comprise the negative electrode that at least one positive electrode is opposite with at least one, this positive and negative counterelectrode alternatively layered and between this counterelectrode, be inserted with separator, be dispersed with electrolyte in this separator, wherein, this positive electrode is made of the metal phosphate active material, and the solvent mixture that this electrolyte comprises slaine and is made up of ethylmethyl carbonate, propylene carbonate, carbonic acid diethyl ester and carbonic acid ethylidene ester.
16. battery pack according to claim 15, wherein, this positive electrode comprises LiMg xFe 1-xPO 4, x is about 0.01 to about 0.15.
17. battery pack according to claim 15, wherein, this positive electrode comprises lithium vanadium phosphate active material.
18. battery pack according to claim 15, wherein, the amount of this ethylmethyl carbonate is about 10 to 80wt%.
19. battery pack according to claim 18, wherein, the amount of this carbonic acid ethylidene ester is about 20 to 80wt%.
20. battery pack according to claim 19, wherein, the amount of this propylene carbonate is about 2 to 20wt%.
21. battery pack according to claim 20, wherein, the amount of this carbonic acid diethyl ester is about 2 to 30wt%.
22. battery pack according to claim 15, wherein, the amount of this ethylmethyl carbonate is about 10 to 40wt%.
23. battery pack according to claim 22, wherein, the amount of this carbonic acid ethylidene ester is about 50 to 70wt%.
24. battery pack according to claim 23, wherein, the amount of this carbonic acid ethylidene ester is about 60wt%.
25. battery pack according to claim 24, wherein, the amount of this propylene carbonate is about 2 to 10wt%.
26. battery pack according to claim 25, wherein, the amount of this propylene carbonate is about 5wt%.
27. battery pack according to claim 26, wherein, the amount of this carbonic acid diethyl ester is about 5 to 30wt%.
28. battery pack according to claim 15, wherein, the amount of this carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate is about 60: 5: 10: 25wt%.
29. battery pack according to claim 15, wherein, the amount of this carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate is about 60: 5: 25: 10wt%.
30. battery pack according to claim 15, wherein, the amount of this carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate is about 60: 5: 5: 30wt%.
31. battery pack according to claim 16, wherein, the amount of this ethylmethyl carbonate is about 10 to 40wt%.
32. battery pack according to claim 31, wherein, the amount of this carbonic acid ethylidene ester is about 30 to 70wt%.
33. battery pack according to claim 32, wherein, the amount of this propylene carbonate is about 2 to 20wt%.
34. battery pack according to claim 33, wherein, the amount of this carbonic acid diethyl ester is about 2 to 30wt%.
35. battery pack according to claim 16, wherein, the amount of this ethylmethyl carbonate is about 10 to 30wt%.
36. battery pack according to claim 35, wherein, the amount of this carbonic acid ethylidene ester is about 50 to 70wt%.
37. battery pack according to claim 36, wherein, the amount of this carbonic acid ethylidene ester is about 60wt%.
38. according to the described battery pack of claim 37, wherein, the amount of this propylene carbonate is about 2 to 10wt%.
39. according to the described battery pack of claim 38, wherein, the amount of this propylene carbonate is about 5wt%.
40. according to the described battery pack of claim 39, wherein, the amount of this carbonic acid diethyl ester is about 5 to 30wt%.
41. battery pack according to claim 16, wherein, the amount of this carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate is about 60: 5: 10: 25wt%.
42. battery pack according to claim 16, wherein, the amount of this carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate is about 60: 5: 25: 10wt%.
43. battery pack according to claim 16, wherein, the amount of this carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate is about 60: 5: 5: 30wt%.
44. battery pack according to claim 17, wherein, the amount of this ethylmethyl carbonate is about 10 to 40wt%.
45. according to the described battery pack of claim 44, wherein, the amount of this carbonic acid ethylidene ester is about 30 to 70wt%.
46. according to the described battery pack of claim 45, wherein, the amount of this propylene carbonate is about 2 to 20wt%.
47. according to the described battery pack of claim 46, wherein, the amount of this carbonic acid diethyl ester is about 2 to 30wt%.
48. battery pack according to claim 17, wherein, the amount of this ethylmethyl carbonate is about 10 to 30wt%.
49. according to the described battery pack of claim 48, wherein, the amount of this carbonic acid ethylidene ester is about 50 to 70wt%.
50. according to the described battery pack of claim 49, wherein, the amount of this carbonic acid ethylidene ester is about 60wt%.
51. according to the described battery pack of claim 50, wherein, the amount of this propylene carbonate is about 2 to 10wt%.
52. according to the described battery pack of claim 51, wherein, the amount of this propylene carbonate is about 5wt%.
53. according to the described battery pack of claim 52, wherein, the amount of this carbonic acid diethyl ester is about 5 to 30wt%.
54. battery pack according to claim 17, wherein, the amount of this carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate is about 60: 5: 10: 25wt%.
55. battery pack according to claim 17, wherein, the amount of this carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate is about 60: 5: 25: 10wt%.
56. battery pack according to claim 17, wherein, the amount of this carbonic acid ethylidene ester, propylene carbonate, carbonic acid diethyl ester and ethylmethyl carbonate is about 60: 5: 5: 30wt%.
57. one kind is used in lithium battery group with lithium metal phosphate cathodes or the electrolyte in the battery, it comprises carbonic acid Methylethyl ester.
58., further comprise carbonic acid ethylidene ester according to the described electrolyte of claim 57.
59., further comprise carbonic acid diethyl ester or dimethyl carbonate according to the described electrolyte of claim 58.
60., further comprise the carbonic acid diethyl ester according to the described electrolyte of claim 57.
61. the application of carbonic acid Methylethyl ester in the electrolyte of lithium battery group with lithium metal phosphate cathodes or battery.
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